Improved detergent and wetting



, PatentedlJune- 21, 1938 rMrnovizn DETERGENT AND raocass on PRODUCING THE AGENT SAME Torsten HasselstromfNew York,

AND WETTING N. Y., assignor to G. & A. Laboratories, Savannah, Ga., a corporation of Georgia I No Drawing.

9 Claims.

This invention relates to an improved detergent and wetting agent and process of producing the same. a.

Many detergents and wetting agents are known, for example soaps, sulfonated castor oil, sulfated higher fatty alcohols of the higher fatty 'acids, sulfonated higher fatty acids, etc.

- these soaps suffer from the disadvantage of being precipitated from their aqueous solutions by the electrolytes in hard water, particularly by waters carrying calcium compounds, and the sulfated higher fatty alcohols, and the fatty acids suffer from the disadvantage of high cost of the higher alcohol used, so that'their use in trade has been severely limited.

The product in accordance with my invention possesses superior detergent and wetting. powers, is economical to manufacture, requires no complicated separation and isolation of the raw ma terial to be sulfonated, and may be madeby a very simple sulfonation process and apparatus. The calcium salts of my not precipitated in hard Broadly speaking, my

water.

trade as Hyex resin and prepared in accordance with the process disclosed in application for United States Letters Patent, Serial No. 6,403, filed February 13, 1935, for Process for the treatment of abietyl compounds and products pro-' duced thereby.

Said application Serial No. 6,403 dicloses the treatment of compounds containing the hydrocarbon nucleus of abietic acid so as to decrease their apparent unsaturated character, and possibly increase their melting points and improve their color, .and also relates to the treated products so formed. Said treatment comprises contactingthe abietyl compound with a catalyst adapted to exclude the possibility of reaction between the abietyl compound and any other material. As a result of such treatment, a change in the chemical and physical properties of the abietyl compound, believed to be due to a simultaneous dehydrogenation and hydrogenation by the heating of the abietyl compound in the presence of the hydrogenation catalyst only, e. g.

sulfonated higher improved detergent are invention comprises the product of the sulforiation of a resin known to the of the type hereinafter described, in a manner Application March 24, 1936, Serial No. 70,672

vention, for example, a catalyst comprising 40% by weight of palladium supported on fibrous asbestos.

' Desirably, the abietyl compound and the catalyst will be brought into contact at an elevated temperature, in order that a practical reaction rate may be obtained, but the use of an elevated temperature is not necessaryfor theaccomplishment of the desired results. The optimum temperature range for the most satisfactory results is from about 150 C. to about 250? G. Since thorough contact between catalyst and abietyl compound can best be compound, when not a liquid at the temperature employed, will be heated to render it liquid.

It-is essential that compound be carried out in such a manner that no reaction can occur between the abletyl compound and any other material. No added hydrogen is present during the treatment. While [the treatment may be carried out in the presence obtained when the abietyl the treatment of the abietyl of air, it is preferable to treat theabietyl com "I rosin,

rosin, alter g treatment 'lhiocyanate No 90-96 10-14 Melting point, drop method -85" C. -90 0. Color Slightly bleached Saponiflcation No 168-172 167-171 Oxygen absorption, percent of total absorbed by 2 double bonds 40% 1% The decrease in the thiocyanate number and ino xygen absorption exhibited by the treated ."If rosin is proof of the marked decrease in apparent chemical unsaturation produced by treatment in accordance with this invention. The fact that the saponiflcation number is practically .the same for both treated and untreated rosins is proof that the carboxyl groups of the rosin acids have been unchanged by the treatment, which must, therefore, effect the hydrocarbon nucleus only.

More specifically,' my invention comprises the of more inert gas, for

- 50 digestion with'aqueous alkali, and crystallization sulfonation by treatment by concentrated sulfuric acid of wood or gum rosin which has been simultaneously dehydrogenated and hydrogenated by heating in the presence of a hydrogenation catalyst, e. g. palladium, in accordance with the process disclosed in application for United States Letters Patent, Serial No. 6,403, and if desired, sulfonation of the resin dissolved in a solvent therefor which is unattacked or attacked by the sulfuric acid, e. g. carbon tetrachloride, liquid sulfur dioxide, petroleum distillate, or unsaturated hydrocarbons and/or alcohols of the aliphatic, alicyclic and/or aromatic type.

As sulfonating agent I preferably employ sulfuric-acid of specific gravity about 1.84, although I may employ somewhat lower strengths of sulfuric acid or somewhat higher strengths, even to fuming sulfuric acid or sulfur trioxide, but at the slight disadvantage of reduced yields of monosulfonic acids, because of side reactions and/or formation of disulfonic acids or mixtures q thereof, I may also employ, if desired, chloroone of the objects of this invention, having a sulfonic" acid aamysuQnating agent.

r V Ewample l As an example of the carrying out of my process, 100 g. of the Hyex resin described above were finely pulverized and added gradually to 200 cc..

of sulfuric acid of specific gravity 1.84 at a temperature of 10 C. with vigorous stirring. The temperature of the mixture rose to 37 C., but

there was no evolution of sulfur dioxide. Sulfonation was complete in 45 minutes, and the temperature dropped to 0., due to the surrounding ice bath used. The mixture was then poured onto ice and the nearly colorless precipitate col: lected, washed with cold-water until the washings clouded when mixed with the original mother liquor. The washed precipitate was extracted once with boiling water. There remained a brownish, insoluble precipitate. The hot aqueous extract, on cooling, separated the sulfonic acid,

melting point of 221-4" C. (with decomposition) or when recrystallized from glacial acetic acid having a melting point of 223-4 C. (with decomposition), ()n= +71.'72, in a yield of 50 g. The yield of the brownish, insoluble product was 47 g.

-This insoluble product may be used as a greasesetting agent or, after removal of acid bodies by of the residue from acetone, yields a solid melting at about 131.5 C. to 132 C. From the alkaline extracts of the brownish, insoluble product, an additional -20% or more of fI-Iyex sulfonic acid can be recovered by acidification. The noncrystalline material, remaining after the removal of these crystalline constituents, I have found to be useful, after refining, e. g. by fractional distillation, as a superior rosin oil in the manufacture of printer's ink, plasticizers, and the like.

Example II In a further example of the carrying out of my invention, 10 g. of the Hyex" resin acid obtained by fractional crystallization of Hyex resin, and having a melting point of about 156 158 C. and an optical rotation (non of about +43.83, was sulfonated at 10-.15 C. with 75 cc.

of 95%.sulfuric acid in a period of 30 minutes,

with vigorous stirring. 'The pale orange solutionresulting was poured into ice water, the precipi tate collected, washed withcold water, extracted twice with boiling water, leaving about 2 g. of insoluble material. The combined aqueous exof 45 minutes.

tracts, on acidification by 10 cc. of concentrated hydrochloric acid, precipitated 7.2 g. of a sulfonic acid melting at 220-3 C. (with decomposition) (a)'D=+61-33, recrystallized from glacial acetic acid, melting at 223-2245? C. (with decomposition).

Example III In a further example of the carrying out of my invention, 10!) g. of distilled Hyex resin,'previously described, was dissolved in 100 cc. of'carously adaptable to uses as an improved detergent aniwetting out agent, e. g. in the scouring of textiles, ififsoapassistant, etc.

I may prepare the neutral 'or acid alkali or alkaline earth, or organic base, e. g. ethaiiola mine, salts of my sulfonic acid product, and such also are variously adaptable to uses as improved detergents and wetting out agents.

The non-crystalline, brownish material separated from the sulfonic acid, as shown, for example, in Examples I and II, I have found useful as a grease-setting and/or emulsifying agent, e. g. in the manufacture of cup grease, solid oils, and the like.

What I claim and desire to protect by Letters Patent is:

1. Method of preparation of a sulfonic acid comprising treating by a sulfonating agent a resin prepared by heat-treating rosin in the presence of a' hydrogenation catalyst and in the absence of added substances capable of reducing the de-' gree of unsaturation of the rosin.

2. Method of preparation of a sulfonic acid comprising treating with concentrated sulfuric acid a resin prepared by heat-treating rosin in the presence of a hydrogenation catalyst and in the absence of added substances capable of reducing the degree of unsaturation of the rosin.

3. Method of preparation of a sulfonic acid comprising treating with concentrated sulfuric acid a solution of a resin' prepared byheat-treating rosinin the presence of a hydrogenationcatalyst and in the absence of added substances capable of reducing the degree of unsaturation of the rosin. i

4. Method of preparation of a sulfonic acid comprising treating with sulfuric acid of sulfonating strength a resin prepared by heat-treating rosin in the presence of a hydrogenation catalyst and in the absence of added substances capable of reducing the degree of unsaturation of the rosin.

5. As a detergent and wetting agent, the sul-' fonic acid obtained by treating a resin prepared by heat-treating rosin in the presence of a hydrogenation catalyst and in the absence of added substances capable of reducing the degree of unsaturation of the rosin with concentrated sulfuric acid. 7

6. As a detergent and wetting agent, compounds of the formula RX, wherein R is the organic radical of the sulfonic acid produced in aiiipaa' I prising the reaction product of the sulfonic acid produced in accordance with claim 1, and an accordance with claim 1, and x is a member of the group consisting of, hydrogen, alkali metals,

alkaline earth metals and alkylol amines.

'1. As adetergent and wetting agent, salts comprising the reaction product of the sulfonic acid produced in accordance with claim 1 and'an ethanolamine.

8. As a detergent and wetting agent, salts comalkali. l

9. As a detergent and wetting agent, salts comprising the reaction product of the sulfonic acid produced in accordance with claim 1, and an alkaline earth.

'rons'nm mssms'mou. 

